CN110337466A - Sensitizing dye, photoelectric conversion sensitizing dye composition, photo-electric conversion element and dye-sensitized solar cell using it - Google Patents

Sensitizing dye, photoelectric conversion sensitizing dye composition, photo-electric conversion element and dye-sensitized solar cell using it Download PDF

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Publication number
CN110337466A
CN110337466A CN201880011818.XA CN201880011818A CN110337466A CN 110337466 A CN110337466 A CN 110337466A CN 201880011818 A CN201880011818 A CN 201880011818A CN 110337466 A CN110337466 A CN 110337466A
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sensitizing dye
carbon atom
substituent group
atom number
changing
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CN110337466B (en
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冈地诚
木村育夫
桦泽直朗
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Baotu Valley Chemical Industry Co Ltd
Hodogaya Chemical Co Ltd
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Baotu Valley Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B15/00—Acridine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B19/00—Oxazine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B21/00—Thiazine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Abstract

A kind of sensitizing dye, photoelectric conversion sensitizing dye composition, photo-electric conversion element and dye-sensitized solar cell using it.It is the new structural sensitizing dye with broad photosensitive wave band by the sensitizing dye that the following general formula (1) indicates, by being used as photoelectric conversion sensitizing dye composition, it is capable of providing photoelectric conversion efficiency high photo-electric conversion element and dye-sensitized solar cell.

Description

Sensitizing dye, photoelectric conversion sensitizing dye composition, the photoelectric conversion element using it Part and dye-sensitized solar cell
Technical field
The present invention relates to sensitizing dye, for sensitizing dye type photo-electric conversion element photoelectric conversion sensitizing dye group It closes object, use the photo-electric conversion element and dye-sensitized solar cell of photoelectric conversion sensitizing dye composition.
Background technique
In recent years, cause from the carbon dioxide that the fossil fuels such as coal, petroleum, natural gas generate as greenhouse gases Global warming, global warming lead to environmental disruption, population increase brings the increase of energy consumption in the world, thus global scale Environmental disruption gradually develops troubling.In response to this, different from fossil fuel and exhausted risk is actively studied The utilization of few renewable energy.Being based on as thermal power generation, the atomic force power generation instead of consumption of fossil fuels can be to anti- The generation mode that the next-generation essential reproducible energy that only global warming is made contributions carries out, centered on solar energy power generating Solar energy gradually risen using its importance, used from wrist-watch, the power generation of portable compact electronic equipment and charging, to can House and building, the fallow ground middle and small scale power generating equipment for the heating fee that saves lighting, exploitation in various fields, using just obtaining Progress.
As solar energy power generating means, the photo-electric conversion element of electric energy is converted solar energy into for solar-electricity Pond, as solar battery, main research has to be changed such as monocrystalline, polycrystalline, amorphous silicon class, GaAs, cadmium sulfide, copper indium diselenide The inorganic solar battery for closing object semiconductor type etc obtains in house, small-scale power generation facility practical extensively at present.But It is that this inorganic solar battery has manufacturing cost height, is difficult to ensure the problems such as raw material.
On the other hand, although photoelectric conversion rate, durability are significant low compared with inorganic solar battery, also Exploitation uses the organics solar-electricities such as organic thin film solar cell, the dye-sensitized solar cell of various organic materials Pond.Organic solar battery is in manufacturing cost, larger in area, lightweight, filming, translucency, the wide scope of absorbing wavelength Change, flexibility, raw material ensure etc., are considered more advantageous than inorganic solar battery.
It wherein, is by as partly leading by the dye-sensitized solar cell (referring to non-patent literature 1) of the propositions such as Gretzel Membrane electrode that body is made of porous titanium oxide, the ruthenium complex dyestuff that semiconductor surface is adsorbed on to expand photosensitive wave band, And the wet type solar battery that the electrolyte comprising iodine is constituted, expect and the matched high photoelectric conversion of non-crystal silicon solar cell Efficiency.Compared with other solar batteries, dye-sensitized solar cell is that component structure is simply set without large size manufacture It is standby to be also able to carry out manufacture, therefore attract attention as next-generation solar battery.
As the sensitizing dye for dye-sensitized solar cell, from photoelectric conversion efficiency this point, ruthenium complex quilt It is considered optimal, but ruthenium is noble metal, therefore unfavorable in terms of manufacturing cost, and works as and be practical and need a large amount of When ruthenium complex, the restriction in resource also becomes problem.Therefore, as sensitizing dye, what is be actively being implemented is using being free of The research of the dye-sensitized solar cell of the organic dyestuff of the noble metals such as ruthenium.It is open as organic dyestuff without precious metal Have Coumarins dyestuff, cyanine class dyestuff, merocyanine class dyestuff, rhodanine class dyestuff, phthalocyanines dye, porphyrin dyestuff, x (for example, referring to Patent Documents 1 to 3) such as ton class dyestuffs.
In addition, as the excitation electronics for being adsorbed on the semiconductor grains such as titanium oxide surface and being generated in sensitizing dye It effectively transports to the electronics suction unit of semiconductor, it is also proposed that the compound with indone structure is (for example, referring to patent document 4~6).But although these organic dyestuff have, cheap, absorptivity is big and it is special to control absorption by Diversity structure The advantage that property, but in terms of photoelectric conversion efficiency and ageing stability, cannot attain full and complete satisfaction required characteristic, this It is status.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 11-214730 bulletin
Patent document 2: Japanese Unexamined Patent Publication 11-238905 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2011-26376 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2011-207784 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2012-51854 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2016-6811 bulletin
Non-patent literature
Non-patent literature 1: " natural (Nature) ", Britain, 1991, volume 353, the 737-740 pages
Summary of the invention
Project to be solved by this invention is to provide a kind of new structural sensitizing dye that can expand photosensitive wave band, And then it is capable of providing a kind of photoelectric conversion sensitizing dye composition that the sensitizing dye is used as and can effectively obtain electric current , the good photo-electric conversion element of light transfer characteristic and dye-sensitized solar cell.
In order to solve the above problems, inventor etc. are furtherd investigate for the light transfer characteristic for improving sensitizing dye As a result, discovery by will have specific structure sensitizing dye be used as photoelectric conversion sensitizing dye, can obtain high efficiency and The photo-electric conversion element of high-durability.That is, the present invention is made of the following contents.
1. sensitizing dye is indicated by the following general formula (1).
[changing 1]
(in formula, Ar indicates can there is the aryl that the carbon atom number of substituent group is 6~36.
R1~R4It is identical or different, and indicate hydrogen atom, halogen atom, cyano, hydroxyl, nitro, nitroso, mercapto,
Can have substituent group carbon atom number be 1~36 straight-chain or branched alkyl,
Can have substituent group carbon atom number be 3~36 naphthenic base,
Can have substituent group carbon atom number be 1~36 straight-chain or branched alkoxy,
Can have substituent group carbon atom number be 3~36 cycloalkyloxy,
Can have substituent group carbon atom number be 2~36 straight-chain or branched alkenyl,
Can have substituent group carbon atom number be 6~36 aryl,
Or can have the amino that the carbon atom number of substituent group is 0~36,
R1~R4It can bond together between adjacent group and form ring.
X indicates sulphur atom, oxygen atom or CR5R6。R5、R6It is identical or different, and indicate the carbon atom that can have substituent group Number is 1~36 straight-chain or the alkyl of branched or can have the aryl that the carbon atom number of substituent group is 6~36.
Z indicates 1 valence base.)
2. sensitizing dye, in the general formula (1), Z is the 1 valence base indicated by the following general formula (2).
[changing 2]
(in formula, R7~R12It is identical or different, and indicate hydrogen atom,
Can have substituent group carbon atom number be 1~18 straight-chain or branched alkyl,
Can have substituent group carbon atom number be 1~18 straight-chain or branched alkoxy,
Or can have the alkenyl of straight-chain or branched that the carbon atom number of substituent group is 2~18,
R7And R8It can bond together and form ring, R9And R10It can bond together and form ring, R11And R12It can be each other It is bonded and forms ring.
M indicates that 0~2 integer, n indicate 0~4 integer, and when the integer that m is 2 or n is 2~4, there are multiple R7 ~R12Among, R7It is same or different to each other between group, R8It is same or different to each other between group, R9It is same or different to each other between group, R10It is same or different to each other between group, R11It is same or different to each other between group, R12It is same or different to each other between group,.
R13And R14Indicate hydrogen atom or acidic groups, R13And R14In at least any one be acidic groups.)
3. the sensitizing dye according to 2, wherein in the general formula (2), R7~R12For hydrogen atom or unsubstituted carbon The alkyl of straight-chain or branched that atomicity is 1~6.
4. according to sensitizing dye described in 2 or 3, wherein in the general formula (2), m is 0 and n is 0.
5. a kind of photoelectric conversion sensitizing dye composition includes the sensitizing dye.
6. a kind of photo-electric conversion element uses photoelectric conversion sensitizing dye composition.
7. a kind of dye-sensitized solar cell uses the photo-electric conversion element.
Sensitizing dye according to the present invention can obtain the photoelectric conversion sensitizing dye group that can effectively obtain electric current Close object.In addition, the photoelectricity that can obtain high efficiency and high-durability turns by using photoelectric conversion sensitizing dye composition Change element and dye-sensitized solar cell.
Detailed description of the invention
Fig. 1 is the fragmentary cross sectional view for indicating the structure of photo-electric conversion element of the embodiment of the present invention and comparative example.
Specific embodiment
Hereinafter, being explained in detail for embodiments of the present invention.The photoelectric conversion being made of sensitizing dye of the invention It is used as sensitizer in the photo-electric conversion element of dye sensitization type with sensitizing dye composition.In addition, in the description of the present application In, " sensitizing dye " refers to that the compound indicated by general formula (1), " photoelectric conversion sensitizing dye composition " refer to comprising one kind Or it is two or more by general formula (1) indicate compounds and include the optional combination for being not belonging to other sensitizing dyes of the invention Object.Photo-electric conversion element of the invention will typically make light made of semiconductor layer of the Dye Adsorption in conductive support Electrode and positioned opposite across electrolyte layer to electrode.
Hereinafter, but the invention is not restricted to this for being specifically described by the sensitizing dye that the general formula (1) indicates.
In general formula (1), as by Ar or R1~R6What is indicated " can have the virtue that the carbon atom number of substituent group is 6~36 " aryl that carbon atom number is 6~36 " in base ", specifically, can enumerate phenyl, naphthalene, xenyl, anthryl, ferrosin base, pyrene The aryl such as base, triethylene, indenyl, fluorenyl.Here, " aryl " in the present invention indicates aromatic hydroxyl and fused polycycle virtue Base, wherein preferably phenyl or naphthyl, more preferably phenyl.
In general formula (1), as by R1~R4" halogen atom " indicated specifically can enumerate fluorine atom, chlorine atom, bromine Atom, iodine atom etc..
In general formula (1), as by R1~R6What is indicated " can have the straight-chain that the carbon atom number of substituent group is 1~36 Or the alkyl of branched " in " carbon atom number be 1~36 straight-chain or branched alkyl ", specifically, can enumerate methyl, The alkyl of the straight-chain of ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl etc.；It is isopropyl, isobutyl group, secondary The alkyl of the branched such as butyl, tert-butyl, iso-octyl.
In general formula (1), as by R1~R4What is indicated " can have the cycloalkanes that the carbon atom number of substituent group is 3~36 " naphthenic base that carbon atom number is 3~36 " in base ", specifically, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, ring The naphthenic base such as heptyl, cyclooctyl, cyclononyl, cyclodecyl.
In general formula (1), as by R1~R4What is indicated " can have the straight-chain that the carbon atom number of substituent group is 1~36 Or the alkoxy of branched " in " carbon atom number be 1~36 straight-chain or branched alkoxy ", specifically, can enumerate: The straight-chains such as methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy, nonyl epoxide, decyloxy Alkoxy；The alkoxy of the branched such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, different octyloxy.
In general formula (1), as by R1~R4What is indicated " can have the cycloalkanes oxygen that the carbon atom number of substituent group is 3~36 " cycloalkyloxy that carbon atom number is 3~36 " in base ", specifically, can enumerate cyclopropyl oxygroup, cyclobutoxy group, cyclopentyloxy, ring The cycloalkyloxies such as hexyloxy.
In general formula (1), as by R1~R4What is indicated " can have the straight-chain that the carbon atom number of substituent group is 2~36 Or the alkenyl of branched " in " carbon atom number be 2~36 straight-chain or branched alkenyl ", specifically, ethylene can be enumerated The straight-chain or branch of the alkenyls such as base, acrylic, isopropenyl, 2- cyclobutenyl, 1- hexenyl or these multiple alkenyls of bonding The alkenyl of shape.
In general formula (1), as by R1~R4" can have the amino that the carbon atom number of substituent group is 0~36 " indicated, Specifically, it can enumerate: unsubstituted amino；Methylamino, dimethylamino, lignocaine, ethylmethylamino, methylpropylamino, It is the amino of 0~36 substituent group that two tertiary fourth amino, diphenylamino etc., which have carbon atom number,.
In general formula (1), as by Ar or R1~R6" aryl that the carbon atom number with substituent group is 6~36 " indicated In " substituent group ", or
By R1~R4" naphthenic base that the carbon atom number with substituent group is 3~36 " of expression,
" alkoxy that the carbon atom number with substituent group is 1~36 straight-chain or branched ",
" with substituent group carbon atom number be 3~36 cycloalkyloxy " or
" substituent group " in " amino that the carbon atom number with substituent group is 0~36 ",
Specifically, it can enumerate: the halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom；
Cyano；Hydroxyl；Nitro；Nitroso；Mercapto；
The carbon atom numbers such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl are 1~30 The alkyl of straight-chain；
The alkyl for the branched that the carbon atom numbers such as isopropyl, isobutyl group, sec-butyl, tert-butyl, iso-octyl are 3~30；
The naphthenic base that the carbon atom numbers such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl are 3~30；
Methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy, nonyl epoxide, decyloxy Etc. carbon atom numbers be 1~30 straight-chain alkoxy；
The branched that the carbon atom numbers such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, different octyloxy are 3~30 Alkoxy；
The cycloalkyloxy that the carbon atom numbers such as cyclopropyl oxygroup, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy are 3~30；
Vinyl, acrylic, isopropenyl, 2- cyclobutenyl, 1- hexenyl or the carbon atom for being bonded these multiple alkenyls Number is 2~30 straight-chain or the alkenyl of branched；
The carbon atom number of phenyl, naphthalene, xenyl, anthryl, phenanthryl, pyrenyl, triphenylene, indenyl, fluorenyl etc. is 6~30 Aryl；
Unsubstituted amino；Methylamino, dimethylamino, lignocaine, ethylmethylamino, methylpropylamino, two tertiary fourths It is the amino of 1~30 substituent group that amino, diphenylamino etc., which have carbon atom number,；
Carboxyl；The carboxylate etc. of carbomethoxy, ethoxycarbonyl etc..These " substituent groups " both may include one, can also be with It, both can be mutually the same or different from each other when comprising multiple comprising multiple.In addition, these " substituent groups " can also be into One step has the substituent group being illustrated above.
In general formula (1), as by R1~R6It indicates
" with substituent group carbon atom number be 1~36 straight-chain or branched alkyl " or
By R1~R4In " alkenyl of straight-chain or branched that the carbon atom number with substituent group is 2~36 " indicated " substituent group ",
Specifically, it can enumerate: the halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom；
Cyano；Hydroxyl；Nitro；Nitroso；Mercapto；
The naphthenic base that the carbon atom numbers such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl are 3~34；
Methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy, nonyl epoxide, decyloxy Etc. carbon atom numbers be 1~34 straight-chain alkoxy；
The branched that the carbon atom numbers such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, different octyloxy are 3~34 Alkoxy；
The cycloalkyloxy that the carbon atom numbers such as cyclopropyl oxygroup, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy are 3~34；
The carbon atom numbers such as phenyl, naphthalene, xenyl, anthryl, phenanthryl, pyrenyl, triphenylene, indenyl, fluorenyl are 6~34 Aryl；
Unsubstituted amino；Methylamino, dimethylamino, lignocaine, ethylmethylamino, methylpropylamino, two tertiary fourths It is the amino of 1~34 substituent group that amino, diphenylamino etc., which have carbon atom number,；
Carboxyl；The carboxylate etc. of carbomethoxy, ethoxycarbonyl etc..These " substituent groups " both may include one, can also be with It, both can be mutually the same or different from each other when comprising multiple comprising multiple.In addition, these " substituent groups " can be into one Walking has the substituent group being illustrated above.
In general formula (1), R1~R4Preferably hydrogen atom, halogen atom, can have substituent group carbon atom number be 1~ The alkyl of 24 straight-chain or branched can have aryl that the carbon atom number of substituent group is 6~24 or can have and takes The amino that the carbon atom number of Dai Ji is 0~24, more preferably hydrogen atom or can to have the carbon atom number of substituent group be 6~24 Aryl.
In general formula (1), R1~R4Indicate substituent group as described above, but can also be between adjacent group each other It is bonded and forms ring, these rings can also be closed by singly-bound or by any of nitrogen-atoms, carbon atom and sulphur atom atom Bonding and bond together, to form ring.These rings are preferably phenyl ring.
In general formula (1), X CR5R6When R5And R6The carbon atom number for being preferably capable having substituent group is 1~24 The alkyl of straight-chain or branched or there can be the aryl that the carbon atom number of substituent group is 6~24, can more preferably have The alkyl of straight-chain or branched that the carbon atom number of substituted base is 1~12.
In general formula (1), Z indicates 1 valence base, the 1 valence base preferably indicated by general formula (2).
In general formula (2), as by R7~R12What is indicated " can have the straight chain that the carbon atom number of substituent group is 1~18 " alkyl of straight-chain or branched that carbon atom number is 1~18 " in the alkyl of shape or branched ", specifically, can enumerate: first The alkyl of the straight-chains such as base, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl；Isopropyl, isobutyl group, The alkyl of the branched such as sec-butyl, tert-butyl, iso-octyl.
In general formula (2), as by R7~R12What is indicated " can have the straight chain that the carbon atom number of substituent group is 1~18 " alkoxy of straight-chain or branched that carbon atom number is 1~18 " in the alkoxy of shape or branched ", specifically, can lift Out: methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy, nonyl epoxide, decyloxy etc. are straight The alkoxy of chain；The alkoxy of the branched such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, different octyloxy.
In general formula (2), as by R7~R12What is indicated " can have the straight chain that the carbon atom number of substituent group is 2~36 " alkenyl of straight-chain or branched that carbon atom number is 2~18 " in the alkenyl of shape or branched ", specifically, can enumerate second The straight-chain of the alkenyl of alkenyl, acrylic, isopropenyl, 2- cyclobutenyl, 1- hexenyl etc. or these multiple alkenyls of bonding or The alkenyl of branched.
In general formula (2), as by R7~R12It indicates
" alkyl that can have the straight-chain or branched that the carbon atom number of substituent group is 1~18 ",
" can have substituent group carbon atom number be 1~18 straight-chain or branched alkoxy " or
" substituent group " in " alkenyl that can have the straight-chain or branched that the carbon atom number of substituent group is 2~18 ",
Specifically, it can enumerate: the halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom；
Cyano；Hydroxyl；Nitro；Nitroso；Mercapto；
The naphthenic base that the carbon atom numbers such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl are 3~16；
Methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy, nonyl epoxide, decyloxy Etc. carbon atom numbers be 1~16 straight-chain alkoxy；
The branched that the carbon atom numbers such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, different octyloxy are 3~16 Alkoxy；
The cycloalkyloxy that the carbon atom numbers such as cyclopropyl oxygroup, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy are 3~16；
The carbon atom numbers such as phenyl, naphthalene, xenyl, anthryl, phenanthryl, pyrenyl, triphenylene, indenyl, fluorenyl are 6~34 Aryl；
Unsubstituted amino；Methylamino, dimethylamino, lignocaine, ethylmethylamino, methylpropylamino, two tertiary fourths It is the amino of 1~16 substituent group that amino, diphenylamino etc., which have carbon atom number,；
Carboxyl；Carboxylates such as carbomethoxy, ethoxycarbonyl etc..These " substituent groups " both may include one, also can wrap It, both can be mutually the same or different from each other when comprising multiple containing multiple.In addition, these " substituent groups " can be further With the substituent group being illustrated above.
In general formula (2), R7~R12Preferably hydrogen atom or can have substituent group carbon atom number be 1~18 straight chain The alkyl of shape or branched, more preferably hydrogen atom.
In general formula (2), R7~R12Indicate substituent group as described above, but can also be between adjacent group each other It is bonded and forms ring, these rings can also be closed by singly-bound or by any of nitrogen-atoms, carbon atom and sulphur atom atom Bonding and bond together, to form ring.
In general formula (2), m and n are respectively indicated with the electron-transport that will evoke in dye moiety to electronics suction unit i.e. The aryl of the effect of the linking group of indone base and the quantity of thienyl.The integer of m expression 0~2, preferably 0 or 1, in addition, n Preferably 0~2, more preferably 0 or 1.
In general formula (2), R13And R14Indicate hydrogen atom or acidic groups, R13And R14In at least any one be acidic groups.As By R13And R14The acidic groups of expression can enumerate carboxyl, sulfonic group, phosphate, hydroxamic acid base, phosphonic acids as specific example Base, boronate, phosphinic acids base, silanol group etc..In these acidic groups, sensitizing dye can be easily adsorbed on semiconductor On the surface of layer, so as to realize raising light transfer characteristic, therefore preferably carboxyl or phosphonic acid base, more preferably carboxyl.
It in the present invention, is all stereoisomers comprising may be present by the sensitizing dye that general formula (1) indicates.It is any vertical Body isomers can be used as the sensitizing dye in the present invention well.For example, Z is to be indicated by general formula (2) in general formula (1) 1 valence base, also, work as R13For hydrogen atom, R14When for carboxyl, sensitizing dye of the invention is comprising by the following general formula (3) and leading to The compound that formula (4) indicates.Alternatively, it is also possible to be from these stereoisomers select two or more mixtures.
[changing 3]
[changing 4]
The specific example of the compound of the sensitizing dye of the invention indicated by general formula (1) is shown in formula below, but It is that the invention is not limited thereto.For example, by general formula (1) although indicate sensitizing dye in X indicate sulphur atom, oxygen atom or CR5CR6, the compound of any one with these is illustrated only in the X section of compound illustrated below, but as example Show compound, is also possible to the compound with other X.In addition, example compound below show may be present solid it is different An example in structure body includes other all stereoisomers.In addition, being respectively also possible to the mixed of two or more stereoisomers Close object.
[changing 5]
[changing 6]
[changing 7]
[changing 8]
[changing 9]
[changing 10]
[changing 11]
[changing 12]
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It can be synthesized by well known method by the sensitizing dye of the invention that general formula (1) indicates.Hereinafter, showing logical The synthesis example for the case where Z is the 1 valence base indicated by general formula (2) in formula (1).In general formula (2), in addition to m is 0 and n is 0 (m=n =0) except the case where, by the bromine compounds with corresponding substituent group indicated by the following general formula (5) and by following logical What formula (6) or the following general formula (7) indicated is respectively provided with the boric acid progress Suzuki coupling reaction of corresponding substituent group and formoxyl Deng cross-coupling reaction, can synthesize by the following general formula (8) indicate formyl adduct.
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In the synthesis example of the formyl adduct indicated by above-mentioned general formula (8), when m is 1 or 2 and n is 0, as tool There is the boric acid of the formoxyl indicated by general formula (6), 4- formyl phenylboronic acid, 4- (4- Fonnylphenyl) phenylboric acid can be enumerated Deng.In addition, in above-mentioned synthesis example, when m is 0 and n is 1~4, as the boric acid with the formoxyl indicated by general formula (7), 5- formoxyl -2- thienyl boric acid or 5'- formoxyl -2,2'- bithiophene -5- boric acid etc. can be enumerated.Moreover, working as, m is 1 or 2 and n is When 1~4, by using the bromine compounds indicated by general formula (5) and there is the formoxyl indicated by above-mentioned identical general formula (7) Boric acid carries out cross-coupling reaction identical with above-mentioned synthesis example, can synthesize the formyl adduct indicated by general formula (8).
In the synthesis example of the formyl adduct indicated by above-mentioned general formula (8), when m is 0 and n is 0 (m=n=0), By the aryl lithium exchanged by the bromine compounds indicated by general formula (5) with progress metal halogens such as butyl lithiums by N, N- diformazan Base formamide (DMF) captures, and thus, it is possible to synthesize the formyl adduct (m=n=0) indicated by general formula (8).
Then, by indicating the formyl adduct indicated by general formula (8) obtained as described above with by general formula (9) Indone compound between carry out condensation reaction, sensitizing dye of the invention can be synthesized.But the general formula in above-mentioned synthesis example (5) Ar and R in~(9)1~R14With the Ar and R in the general formula (1) and general formula (2) in the present invention1~R14It indicates identical to contain Justice.Thus, in general formula (5)~(9), when m or n is multiple, there are multiple R7~R12In, R7Group, R8Group, R9Group, R10 Group, R11Group, R12Group both can be the same or different respectively, R13And R14Indicate hydrogen atom or acidic groups, R13And R14In at least Any one is acidic groups.
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In addition, both having can be used in the market, also having can be used logical about the above-mentioned formula (5) etc. for becoming initial feed Cross well known method synthesis.It can be by remembering in patent document 4~6 above-mentioned by the indone compound that above-mentioned general formula (9) indicate The method of load is easily synthesized.
The refining methd of compound as the sensitizing dye of the invention indicated by general formula (1), can enumerate: according to column color Compose the purification of purifying；Adsorption refining based on the progress such as silica gel, active carbon, atlapulgite；Recrystallization, the knot carried out based on solvent The known methods such as crystallization.In addition, the identification of these compounds can be carried out by nuclear magnetic resonance spectroscopy (NMR) etc..
Sensitizing dye of the invention both may be used alone, can also be used in combination two or more.In addition, increasing of the invention Infection material can be applied in combination with other sensitizing dyes of the invention are not belonging to.It, can as the specific example of other sensitizing dyes Enumerate ruthenium complex, Coumarins dyestuff, cyanine class dyestuff, merocyanine class dyestuff, rhodanine class dyestuff, phthalocyanines dye, porphin The sensitizing dye in addition to the sensitizing dye indicated by the general formula (1) such as quinoline class dyestuff, x tons of class dyestuffs.When increasing of the invention When infection material combines with these other sensitizing dyes and is used as photoelectric conversion sensitizing dye composition, for increasing sense of the invention The usage amount of other sensitizing dyes of dyestuff is preferably 10~200 weight %, more preferably 20~100 weight %.
Sensitizing dye of the invention can be applied as silver halide, zinc oxide, titanium oxide etc., the sense for various image forming materials The spectral sensitizing dyes such as stimulative substance, photochemical catalyst, optical functional materials, to also can be applied as the light for dye sensitization type The photoelectric conversion of electric transition element etc. sensitizing dye composition etc..The photoelectric conversion element of dye sensitization type is manufactured in the present invention The method of part is not particularly limited, it is preferred that following methods: being formed semiconductor layer on conductive support (electrode), is made this The photoelectric conversion of invention sensitizing dye composition adsorbs (bearing) in the semiconductor layer, to make optoelectronic pole (referring to Fig.1. Furthermore, it will nevertheless be understood that figure be in order to be interpreted as preferential, therefore be not the full-size(d) of actual components).As making dyestuff Semiconductor layer is usually immersed in the side in the solution as obtained from dyestuff is dissolved in solvent by the method for absorption for a long time Method.It is two or more or by sensitizing dye of the invention and other sensitizing dyes when sensitizing dye of the invention to be applied in combination When being applied in combination, the mixed solution of used all dyestuffs can be prepared to impregnate semiconductor layer, alternatively, it is also possible to for each A dyestuff prepares different solution, and semiconductor layer is successively impregnated in each solution.
In the present invention, as conductive support, other than metallic plate, it also can be used to be provided with to have on surface and lead Glass substrate, the plastic base of the conductive layer of electric material.As the specific example of conductive material, can enumerate gold, silver, copper, Conductive clears oxide semiconductor, the carbon such as the metals such as aluminium, platinum, tin oxide, the indium tin composite oxides for adulterating fluorine etc., preferably make With the glass substrate for the SnO 2 thin film for being coated with doping fluorine.
In the present invention, the specific example as the semiconductor for forming semiconductor layer, can enumerate: titanium oxide, zinc oxide, oxygen Change the metal oxides such as tin, indium oxide, zirconium oxide, tungsten oxide, tantalum oxide, iron oxide, gallium oxide, nickel oxide, yttrium oxide；Vulcanization The metal sulfides such as titanium, zinc sulphide, vulcanization zirconium, copper sulfide, artificial gold, indium sulfide, tungsten sulfide, cadmium sulfide, silver sulfide；Selenizing The metal selenides such as titanium, selenizing zirconium, indium selenide, tungsten selenide；Monolithic semiconductors such as silicon, germanium etc..These semiconductors not only can be single It solely uses, two or more uses can also be mixed.In the present invention, as semiconductor, preferably from titanium oxide, zinc oxide, oxygen Change the one or more kinds of uses of tin selection.
The form of semiconductor layer in the present invention is not particularly limited, however, it is preferred to be porous with what is be made of particle The film of structure.By porous structure etc., the actual surface area of semiconductor layer increases, if the Dye Adsorption amount to semiconductor layer increases Greatly, then efficient photo-electric conversion element can be obtained.Semiconductor partial size is preferably 5~500nm, more preferably 10~100nm. The film thickness of semiconductor layer is usually 2~100 μm, and more preferably 5~20 μm.As the production method of semiconductor layer, can enumerate Contained on conductive board by the coating of the wet coatings methods such as method of spin coating, scraper membrane formation process, brushing method, silk screen print method After the slurry of semiconductive particles, the method being film-made and roasting to remove solvent, additive, by sputtering method, vapour deposition method, Methods of films such as electrodeposition process, electric deposition method, microwave irradiation etc., but not limited to this.
In the present invention, the slurry containing semiconductive particles can be used in the market, also can be used by by market On semiconductor microactuator powder be scattered in solvent and the slurry etc. for preparing.Concrete example as the solvent used when preparing slurry Son can enumerate water；The alcohols solvents such as methanol, ethyl alcohol, isopropanol；The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) are molten Agent；The hydrocarbon solvents such as n-hexane, hexamethylene, benzene, toluene, but not limited to this.In addition, these solvents can be used alone or with Two or more mixed solvents uses.
In the present invention, it is scattered in the method in solvent as by semiconductor microactuator powder, the abrasive flours such as mortar can be used It carries out later, the dispersion machines such as ball mill, paint conditioner, vertical type pearl-grinding machine, Horizontal sand mill, grater also can be used.System Preferably addition is for preventing the surfactant etc. of semiconductive particles cohesion when standby slurry, and preferably addition is for the poly- of thickening The thickeners such as ethylene glycol.
About can for example pass through in the semiconductor layer surface to photoelectric conversion sensitizing dye composition of the invention Semiconductor layer is immersed in the dye solution, place 30 minutes~100 hours at room temperature or is placed in a heated condition It 10 minutes~24 hours carries out.In this case, it is preferable to the dye to place 10~20 hours at room temperature, in the dye solution Expect that concentration is preferably 10~2000 μM, more preferably 50~500 μM.
It is molten as what is used when being adsorbed on photoelectric conversion of the invention in semiconductor layer surface with sensitizing dye composition Agent can specifically enumerate: the alcohols solvent of methanol, ethyl alcohol, isopropanol, tert-butyl alcohol etc.；Acetone, methyl ethyl ketone, methyl tert-butyl The ketones solvents such as base ketone；The esters solvents such as Ethyl formate, ethyl acetate, n-butyl acetate；Ether, 1,2- dimethoxy-ethane, The ether solvents such as tetrahydrofuran, 1,3- dioxolanes；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl -2- pyrrole The amide solvents such as pyrrolidone；The nitrile solvents such as acetonitrile, methoxyacetonitrile, propionitrile；Methylene chloride, chloroform, bromofom, o-dichlorohenzene Equal halogenated hydrocarbon solvents；Hydrocarbon solvents such as n-hexane, hexamethylene, benzene, toluene etc., but not limited to this.These solvents individually make It is used with or with two or more mixed solvents.In these solvents, it is preferable to use from methanol, ethyl alcohol, the tert-butyl alcohol, acetone, The one or more that methyl ethyl ketone, tetrahydrofuran, acetonitrile select.
It, can also be by gallbladder when photoelectric conversion of the invention to be adsorbed in semiconductor layer surface with sensitizing dye composition The chlolic acid derivatives such as acid or deoxycholic acid, chenodesoxycholic acid, lithocholic acid, dehydrocholic acid are dissolved in dye solution, total with dyestuff Absorption.By using cholic acid or chlolic acid derivatives, inhibit the polymerization between dyestuff, in photo-electric conversion element can from dyestuff to Semiconductor layer is effectively injected electronics.When using cholic acid or chlolic acid derivatives, the concentration in dye solution is preferably 0.1 ~100mM, more preferably 0.5~10mM.
As for photo-electric conversion element of the invention to electrode (electrode), as long as conductive substance, just It is not particularly limited, but in order to promote the redox reaction of redox ion, it is preferable to use with catalytic capability Conductive material.As the specific example of the conductive material, platinum, rhodium, ruthenium, carbon etc. can be enumerated, but not limited to this.In this hair In bright, especially preferably the substance that platinum film is formed in conductive support is used as to electrode.In addition, thin as electric conductivity The manufacturing method of film can be enumerated: pass through method of spin coating, scraper membrane formation process, brushing method, silk screen print method on conductive board Etc. wet coatings method coating the slurry containing conductive material after, be film-made and roasting to remove solvent, additive Method；By methods of films such as sputtering method, vapour deposition method, electrodeposition process, electric deposition method, microwave irradiation etc., but it is not limited to This.
In photo-electric conversion element of the invention, electrolyte is filled between a pair of opposite electrode, to form electrolysis Matter layer.As used electrolyte, preferably redox electrolyte.As redox electrolyte, can enumerate iodine, bromine, The redox ions pair such as tin, iron, chromium, anthraquinone, but not limited to this.In these, preferably iodine class electrolyte, bromine class are electrolysed Matter.In the electrolytelike situation of iodine, for example, using the mixed of potassium iodide, lithium iodide, iodate dimethylimidazolium iodide etc. and iodine Close object.In the present invention, it is preferred to using by these electrolyte dissolutions electrolyte obtained from solvent.Electrolyte in electrolyte Concentration be preferably 0.05~5M, more preferably 0.2~1M.
As the solvent of dissolution electrolyte, can enumerate: acetonitrile, methoxyacetonitrile, propionitrile, 3- methoxypropionitrile, benzonitrile etc. Nitrile solvents；The ether solvents such as ether, 1,2- dimethoxy-ethane, tetrahydrofuran；N,N-dimethylformamide, N, N- dimethyl The amide solvents such as acetamide；The carbonates solvent such as ethylene carbonate, propylene carbonate；Gamma-butyrolacton, gamma-valerolactone etc. Lactone solvent, but not limited to this.These solvents are used alone or are used with two or more mixed solvents.In these solvents In, preferably nitrile solvents.
In the present invention, in order to further increase the open-circuit voltage and fill factor of dye-sensitized photoelectric conversion device, Aminated compounds can also be contained in the electrolyte.As aminated compounds, 4- tert .-butylpyridine, 4- methyl pyrrole can be enumerated Pyridine, 2- vinylpyridine, N, N- dimethyl -4-aminopyridine, N, accelerine, N- tolimidazole etc..Electrolyte In the concentration of aminated compounds be preferably 0.05~5M, more preferably 0.2~1M.
As the electrolyte in photo-electric conversion element of the invention, it can be used and obtained by addition gelling agent, polymer etc. The gelated electrolyte that arrives, using the solid electrolyte of the polymer such as polyethylene oxide derivant.By using gelated electrolyte, admittedly Body electrolyte can reduce the volatilization of electrolyte.
In photo-electric conversion element of the invention, and it also can replace electrolyte between a pair of opposite electrode and formed admittedly Bulk charge transport layer.It include charge transport materials in solid charge transport layer is preferably hole transporting material.As charge The specific example of transport materials can be enumerated: the inorganic holes transport materials such as cupric iodide, copper bromide, cupric thiocyanate；Polypyrrole gathers Thiophene, p-phenylene vinylene, polyvinylcarbazole, polyaniline, oxadiazole derivatives, triphenylamine derivative, pyrazoline derivative, Fluorenone The organic holes transport materials such as derivative, hydrazone compound, stilbene compounds, but not limited to this.
In the present invention, when forming solid charge transport layer using organic hole transport materials, film can be applied in combination Formative adhesive resin.As the specific example of film formative adhesive resin, polystyrene resin, polyvinyl alcohol can be enumerated Acetal resin, polycarbonate resin, polysulfone resin, polyester resin, polyphenylene oxide resin, polyarylate resin, alkyd resin, acrylic acid Resin, phenoxy resin etc., but not limited to this.These resins can be used alone or as copolymer in combination use it is a kind of or It is two or more.Usage amount for the organic hole transport materials of these adhesive resins is preferably 20~1000 weight %, more Preferably 50~500 weight %.
In photo-electric conversion element of the invention, it is provided with the semiconductor for being adsorbed with photoelectric conversion sensitizing dye composition The electrode (optoelectronic pole) of layer becomes cathode, becomes anode to electrode.The light such as sunlight can be from optoelectronic pole side, appoint electrode side Side irradiation, it is preferred that be irradiated from optoelectronic pole side.By the irradiation of sunlight etc., dyestuff absorbs light and becomes excitation shape State discharges electronics.The electronics flows to outside via semiconductor layer, thus to electrode movement.On the other hand, discharge electronics and Dyestuff as the state of oxidation is received via the ion in electrolyte from the electronics supplied to electrode, to be restored to substrate shape State.By the circulation, electric current flowing is used as photo-electric conversion element.
When evaluating performance (characteristic) of photo-electric conversion element of the invention, carry out short circuit current, open-circuit voltage, filling because The measurement of son, photoelectric conversion efficiency.Short circuit current expression makes every 1cm of flowing when output terminal short circuit between two-terminal2 Electric current, open-circuit voltage indicates the voltage between two-terminal when output terminal is opened a way.In addition, fill factor refers to that maximum is defeated (product of circuit and voltage) depends primarily on internal resistance divided by the value of short circuit current and open-circuit voltage product out.Photoelectric conversion effect Rate by maximum output (W) divided by every 1cm2Luminous intensity (W) value on be expressed as the value of percentage multiplied by 100 to ask Out.
Photo-electric conversion element of the invention can be applied to dye-sensitized solar cell, various optical sensors etc..This hair Bright dye-sensitized solar cell obtains as follows: containing and includes the photoelectric conversion of the sensitizing dye indicated by the general formula (1) Become unit with the photo-electric conversion element of sensitizing dye composition, which is arranged in requirement and modularity, setting is pre- Fixed electric wiring.
Embodiment
Hereinafter, the present invention is illustrated by embodiment, but the present invention is not limited to the following embodiment.In addition, In synthetic example, the identification of compound passes through1H-NMR analysis (nuclear magnetic resonance device anufactured by Japan Electron Optics Laboratory(JEOL), JNM-ECA-600 it) carries out.
The synthesis of [synthetic example 1] sensitizing dye (A-4)
In the reaction vessel of nitrogen displacement, the dehydration for the bromine compounds, 16mL of 1.20g indicated by following formula (10) is added Tetrahydrofuran is stirred at -72 DEG C and instills the lithium hexane solution of the 1.6M of 1.5mL, carries out reaction 1 hour. After reaction, the dehydration dimethylformaldehyde of 0.3mL is instilled in reaction solution, carries out reaction 2 hours.Reaction solution is poured into 50mL's In ice water, organic layer is extracted with salinization methylene chloride.After washing organic layer, separated, it is dry with magnesium sulfate, subtract Pressure concentration, obtains crude product.Crude product is passed through into chromatographic column (carrier: silica gel, eluent: hexane/toluene=9/1 (volume ratio)) It is refined, obtains the yellow solid (0.78g) of the formyl adduct indicated by following formula (11).
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Nitrogen displacement reaction vessel in, be added 0.300g by above formula (11) indicate formyl adduct, 0.179g by following formula (12) indicate indone compound, 13.5mL acetic acid/toluene=5/2 (volume ratio) mixed liquor, 90 It is stirred 3 hours at DEG C.After reaction solution is cooled to 25 DEG C, the water that 50mL is added is stirred, and extracts organic layer.It will be organic Layer water and saturated salt solution successively clean, are dry, obtain target sensitizing dye (0.294g, the yield of violet solid 75%).
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NMR analysis is carried out to obtained violet solid, 26 hydrogen signals below is detected, identifies as by following formula (A-4) The structure (not observing the hydrogen of carboxyl) of expression.
1H-NMR(600MHz、CDCl3): δ (ppm)=6.01-6.05 (2H), 6.90-6.95 (2H), 7.05-7.08 (1H)、7.23-7.27(5H)、7.30-7.40(8H)、7.42-7.50(2H)、7.55-7.65(1H)、7.94-8.01(2H)、 8.28-8.32(1H)、8.36-8.40(1H)、8.50-8.55(1H)。
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The synthesis of [synthetic example 2] sensitizing dye (A-10)
In the reaction vessel of nitrogen displacement, the bromine compounds of the 1.50g indicated by above formula (10), the first of 30mL is added Benzene, the ethyl alcohol of 8mL, the water of 8mL, the 5'- formoxyl -2,2'- bithiophene -5- boric acid of 0.81g, the potassium carbonate of 0.62g and stirring 5 Hour, after stirring, the decompression, degassing, the nitrogen displacement that are repeated 3 times in reaction vessel.Then, the four (triphenyls of 0.18g are added Phosphine) palladium, is stirred 5 hours at 80 DEG C.After reaction solution is cooled to 25 DEG C, be added the ethyl acetate of 10mL, 30mL water into Row stirring, extracts organic layer.Organic layer is dry with magnesium sulfate, it is concentrated under reduced pressure, obtains crude product.Crude product is passed through into chromatography Column (carrier: silica gel, eluent: chloroform/hexane=3/1 (volume ratio)) is refined, and the formyl indicated by following formula (13) is obtained The Tan solid (1.20g) of based compound.
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In the reaction vessel of nitrogen displacement, the formyl adduct indicated by above formula (13), the 13.5mL of 0.64g is added Acetic acid/toluene=5/2 (volume ratio) mixed liquor, 0.29g by above formula (12) indicate indone compound, stirred at 90 DEG C 3 hours.After reaction solution is cooled to 25 DEG C, the water that 80mL is added is stirred, and extracts organic layer.By organic layer water with And saturated salt solution successively cleans, is dry, obtains the target sensitizing dye (0.53g, yield 65%) of black solid.
NMR analysis is carried out to obtained black solid, 30 hydrogen signals below is detected, identifies as by following formula (A-10) The structure (not observing the hydrogen of carboxyl) of expression.
1H-NMR(600MHz、CDCl3): δ (ppm)=5.96-6.06 (1H), 6.08-6.18 (1H), 6.85-6.95 (3H)、6.94-7.04(1H)、7.04-7.14(4H)、7.15-7.25(3H)、7.32-7.42(2H)、7.46-7.56(9H)、 7.66-7.76(1H)、7.78-7.88(2H)、8.06-8.16(1H)、8.57-8.67(2H)。
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The synthesis of [synthetic example 3] sensitizing dye (A-51)
In the reaction vessel of nitrogen displacement, the dehydration for the bromine compounds, 30mL of 2.0g indicated by following formula (14) is added Tetrahydrofuran is stirred at -72 DEG C and instills the lithium hexane solution of the 1.6M of 3.0mL, carries out reaction 1 hour. After reaction, the dehydration dimethylformaldehyde of 0.6mL is instilled in reaction solution, carries out reaction 2 hours.Later, reaction solution is poured into In the ice water of 150mL, organic layer is extracted with salinization methylene chloride.Organic layer is washed, is separated, decompression dry with magnesium sulfate Concentration.Residue is refined by chromatographic column (carrier: silica gel, solvent: hexane/toluene=9/1 (volume ratio)), is obtained under The white-yellowish solid (0.99g) for the formyl adduct that formula (15) indicates.
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Nitrogen displacement reaction vessel in, be added 0.300g by above formula (15) indicate formyl adduct, 0.150g by above formula (12) indicate indone compound, 13.5mL acetic acid/toluene=5/2 (volume ratio) mixed liquor, 90 It is stirred 4 hours at DEG C.After reaction solution is cooled to 25 DEG C, the toluene that 30mL is added is stirred, and extracts organic layer.Use water And saturated salt solution successively cleans, and obtained organic layer is dry, obtain the target sensitizing dye of dark brown solid (0.286g, yield 74%).
NMR analysis is carried out to obtained dark brown solid, 30 hydrogen signals below is detected, identifies as by following formula (A- 51) structure (not observing the hydrogen of carboxyl) indicated.
1H-NMR(600MHz、CDCl3): δ (ppm)=1.87-1.90 (6H), 6.34-6.39 (2H), 7.33-7.36 (1H)、7.39-7.42(1H)、7.44-7.48(3H)、7.54-7.60(4H)、7.66-7.69(2H)、7.82-7.86(4H)、 7.99-8.02(3H)、8.03-8.08(1H)、8.12-8.20(1H)、8.30-8.40(2H)。
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The synthesis of [synthetic example 4] sensitizing dye (A-60)
In the reaction vessel of nitrogen displacement, the bromine compounds of 0.55g indicated by above formula (14), the 5- of 0.197g is added Formoxyl -2- thienyl boric acid, the dimethyl sulfoxide of 20mL, the potassium carbonate of 0.124g and stirring 5 hours, after stirring, are repeated 5 times Decompression, degassing, nitrogen displacement in reaction vessel.Then, bis- (the 1- Buddha's warrior attendants of the butyl of acid chloride, 0.038g that 0.012g is added Alkyl) phosphine, decompression, degassing, the nitrogen displacement being repeated 5 times in reaction vessel.Later, it is stirred 3 hours at 75 DEG C.By reaction solution It is cooled to after 25 DEG C, the water of chloroform, 60mL that 150mL is added is stirred, and extracts organic layer.By organic layer magnesium sulfate It is dry, it is concentrated under reduced pressure, obtains crude product.Crude product is passed through into chromatographic column (carrier: silica gel, eluent: hexane/toluene=1/4 (volume ratio)) it refined, dried, obtain the yellow solid (0.543g) of the formyl adduct indicated by following formula (16).
[changing 81]
Nitrogen displacement reaction vessel in, be added 0.542g by above formula (16) indicate formyl adduct, 0.256g by above formula (12) indicate indone compound, 28mL acetic acid/toluene=5/2 (volume ratio) mixed liquor, at 90 DEG C Lower stirring 10 hours.After reaction solution is cooled to 25 DEG C, the toluene that 50mL is added is stirred, and extracts organic layer.Use water And saturated salt solution successively cleans, and obtained organic layer is dry, obtain the target sensitizing dye of red brown solid (0.453g, yield 67%).
NMR analysis is carried out to obtained red brown solid, 32 hydrogen signals below is detected, identifies as by following formula (A- 60) structure (not observing the hydrogen of carboxyl) indicated.
1H-NMR(600MHz、CDCl3): δ (ppm)=1.82-1.86 (6H), 6.32-6.40 (2H), 7.30-7.35 (1H)、7.35-7.40(1H)、7.41-7.49(3H)、7.53-7.59(5H)、7.64-7.69(2H)、7.80-7.88(4H)、 8.00-8.10(5H)、8.27-8.34(2H)、8.36-8.40(1H)。
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The synthesis of [synthetic example 5] sensitizing dye (A-48)
Instead of the raw material 5- formoxyl -2- thienyl boric acid in synthetic example 4,4- formylphenylboronic acid has been used, has removed this Except, it is synthesized in a manner of identical with synthetic example 4, obtains target sensitizing dye (0.486g, the yield of red brown solid 75%).
NMR analysis is carried out to obtained red brown solid, 34 hydrogen signals below is detected, identifies as by following formula (A- 48) structure (not observing the hydrogen of carboxyl) indicated.
1H-NMR(600MHz、CDCl3): δ (ppm)=1.83-1.87 (6H), 6.31-6.39 (2H), 7.28-7.34 (1H)、7.33-7.39(1H)、7.41-7.49(3H)、7.53-7.60(5H)、7.63-7.68(2H)、7.81-7.88(3H)、 7.92-7.99(3H)、8.01-8.08(4H)、8.34-8.41(1H)、8.41-8.45(1H)、8.63-8.69(2H)。
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The synthesis of [synthetic example 6] sensitizing dye (A-61)
Nitrogen displacement reaction vessel in, be added 0.251g by following formula (17) indicate formyl adduct, 0.124g by above formula (12) indicate indone compound, 15mL acetic acid/toluene=5/2 (volume ratio) mixed liquor, at 90 DEG C Lower stirring 6 hours.After reaction solution is cooled to 25 DEG C, the toluene that 30mL is added is stirred, and extracts organic layer.With water with And saturated salt solution successively cleans, obtained organic layer is dry, obtain reddish violet solid target sensitizing dye (0.268g, Yield 87%).
[changing 84]
NMR analysis is carried out to obtained reddish violet solid, 34 hydrogen signals below is detected, identifies as by following formula (A- 61) structure (not observing the hydrogen of carboxyl) indicated.
1H-NMR(600MHz、CDCl3): δ (ppm)=1.50-1.54 (6H), 1.76-1.80 (6H), 6.31-6.40 (2H)、7.31-7.36(1H)、7.38-7.48(6H)、7.62-7.67(1H)、7.65-7.70(2H)、7.71-7.76(1H)、 7.80-7.84(1H)、7.87-7.92(1H)、7.96-8.08(2H)、8.12-8.23(2H)、8.28-8.37(1H)、8.35- 8.41(1H)、9.22-9.28(1H)。
[changing 85]
The synthesis of [synthetic example 7] sensitizing dye (A-62)
Instead of the bromine compounds indicated by above formula (14) in synthetic example 4, the bromine indicated by following formula (18) has been used In addition to this compound is synthesized in a manner of identical with synthetic example 4, obtain the formoxyl chemical combination indicated by following formula (19) Object.
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Nitrogen displacement reaction vessel in, will by above formula (19) indicate formyl adduct with synthetic example 4 Identical mode is reacted with the indone compound indicated by above formula (12), obtains the target sensitizing dye of violet solid (0.37g, yield 73%).
NMR analysis is carried out to obtained violet solid, 36 hydrogen signals below is detected, identifies as by following formula (A-62) The structure (not observing the hydrogen of carboxyl) of expression.
1H-NMR(600MHz、CDCl3): δ (ppm)=1.50-1.54 (6H), 1.83-1.87 (6H), 6.32-6.38 (2H)、7.28-7.34(1H)、7.33-7.38(1H)、7.38-7.47(5H)、7.50-7.56(1H)、7.61-7.71(4H)、 7.77-7.82(1H)、7.83-7.87(1H)、7.94-8.02(3H)、8.03-8.07(1H)、8.16-8.21(1H)、8.25- 8.32(2H)、8.33-8.40(1H)。
[changing 88]
[embodiment 1]
On the glass substrate of SnO 2 thin film for being coated with doping fluorine, by scraper plate method coated with titanium oxide slurry, (day is waved Catalyst is melted into the PST-18NR of Co., Ltd.'s manufacture).At 110 DEG C after drying 1 hour, roasts 30 minutes, obtain at 450 DEG C The thin film of titanium oxide that film thickness is 6 μm.Then, the sensitizing dye obtained in synthetic example 1 (A-4) is dissolved in acetonitrile/uncle In the mixed liquor of butanol=1/1 (volume ratio), so that the solution that the concentration for preparing 50mL is 100 μM will be coated in the solution The glass substrate of sintering oxidation titanium impregnates 15 hours at 25 ± 2 DEG C and adsorbs dyestuff, is used as optoelectronic pole.
Automatic fine coating machine (Japan Electronics strain formula is used on the glass substrate of SnO 2 thin film for being coated with doping fluorine The JFC-1600 of commercial firm's manufacture), the platinum film that film thickness is 15nm is formed by sputtering method, is used as to electrode.
Then, pass through heat in optoelectronic pole and between electrode centre will be placed in a thickness of 60 μm of spacer (heat fusion film) Fusion is engaged, to electrode hole injection electrolyte (lithium iodide of 0.1M, 0.6M dimethyl propyl imidazolium iodide, The 4- tert .-butylpyridine of the iodine of 0.05M, 0.5M)/3- methoxypropionitrile solution) after sealing hole, produce photo-electric conversion element.
From the optoelectronic pole side of the photo-electric conversion element, irradiation passes through simulated solar light irradiation device (spectrometer Co., Ltd. The OTENTO-SUN type III of manufacture) light that generates, use the source table 2400 type universal source tables of manufacture (KEITHLEY) measurement electricity Stream-voltage characteristic.The intensity of light is adjusted to 100mW/cm2.Obtained measurement result and initial photoelectric conversion efficiency are shown In table 1.In addition, by the photoelectric conversion efficiency also measured in the same way for the characteristic variations after irradiation light 20 hours As a result summarize and show in table 1.
[2~embodiment of embodiment 11]
As photoelectric conversion sensitizing dye, instead of (A-4) respectively using sensitizing dye shown in table 1, for except this Except the I-E characteristic of the photo-electric conversion element prepared in the same manner as example 1, initial and irradiation light 20 Photoelectric conversion efficiency after hour, which summarizes, to be shown in table 1.
[1~comparative example of comparative example 5]
As photoelectric conversion sensitizing dye, is used instead of (A-4) and be not belonging to (B-1) below~(B-5) of the invention Shown in sensitizing dye, the electric current-about the photo-electric conversion element prepared in the same manner as example 1 in addition to this Voltage characteristic, the initial and photoelectric conversion efficiency after irradiation light 20 hours, which summarize, to be shown in table 1.
[changing 89]
[changing 90]
[changing 91]
[changing 92]
[changing 93]
[table 1]
As can be known from the results of Table 1, it is combined by using the photoelectric conversion containing sensitizing dye of the invention with sensitizing dye Object can obtain photoelectric conversion efficiency height and be able to maintain the photoelectric conversion element of photoelectric conversion efficiency long-time irradiation light Part.On the other hand, the photoelectric conversion efficiency using the photo-electric conversion element of the photoelectric conversion sensitizing dye of comparative example is insufficient.
INDUSTRIAL APPLICABILITY
The photoelectric conversion sensitizing dye composition being made of sensitizing dye of the invention has for high efficiency and high durable The photo-electric conversion element and dye-sensitized solar cell of property, as the sun that can effectively convert solar energy into electric energy Energy battery, is capable of providing clean energy resource.
Description of symbols
1 conductive support；2 dyestuff bearing semiconductor layers；3 electrolyte layers；4 pairs of electrodes；5 conductive supports.

Claims (7)

1. a kind of sensitizing dye is indicated by the following general formula (1),
[changing 1]
In formula, Ar indicates can there is the aryl that the carbon atom number of substituent group is 6~36,
R1~R4It is identical or different, and indicate hydrogen atom, halogen atom, cyano, hydroxyl, nitro, nitroso, mercapto,
Can have substituent group carbon atom number be 1~36 straight-chain or branched alkyl,
Can have substituent group carbon atom number be 3~36 naphthenic base,
Can have substituent group carbon atom number be 1~36 straight-chain or branched alkoxy,
Can have substituent group carbon atom number be 3~36 cycloalkyloxy,
Can have substituent group carbon atom number be 2~36 straight-chain or branched alkenyl,
Can have substituent group carbon atom number be 6~36 aryl,
Or can have the amino that the carbon atom number of substituent group is 0~36,
R1~R4It can bond together between adjacent group and form ring,
X indicates sulphur atom, oxygen atom or CR5R6, R5、R6It is identical or different, and indicating to have the carbon atom number of substituent group is 1 ~36 straight-chain or the alkyl of branched or can have substituent group carbon atom number be 6~36 aryl,
Z indicates 1 valence base.
2. sensitizing dye according to claim 1, wherein
In the general formula (1), Z is the 1 valence base indicated by the following general formula (2),
[changing 2]
In formula, R7~R12It is identical or different, and indicate hydrogen atom,
Can have substituent group carbon atom number be 1~18 straight-chain or branched alkyl,
Can have substituent group carbon atom number be 1~18 straight-chain or branched alkoxy,
Or can have the alkenyl of straight-chain or branched that the carbon atom number of substituent group is 2~18,
R7And R8It can bond together and form ring, R9And R10It can bond together and form ring, R11And R12It can bond together And ring is formed,
M indicates that 0~2 integer, n indicate 0~4 integer, and when the integer that m is 2 or n is 2~4, there are multiple R7~R12 Among, R7It is same or different to each other between group, R8It is same or different to each other between group, R9It is same or different to each other between group, R10Group Between be same or different to each other, R11It is same or different to each other between group, R12It is same or different to each other between group,
R13And R14Indicate hydrogen atom or acidic groups, R13And R14In at least any one be acidic groups.
3. sensitizing dye according to claim 2, wherein
In the general formula (2), R7~R12The straight-chain or branched for being 1~6 for hydrogen atom or unsubstituted carbon atom number Alkyl.
4. sensitizing dye according to claim 2 or 3, wherein
In the general formula (2), m is 0 and n is 0.
5. a kind of photoelectric conversion sensitizing dye composition includes sensitizing dye described in any one of Claims 1-4.
6. a kind of photo-electric conversion element uses the sensitizing dye composition of the photoelectric conversion described in claim 5.
7. a kind of dye-sensitized solar cell uses photo-electric conversion element as claimed in claim 6.
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